EP1037960B1 - Corps moules de detergent a desintegration amelioree - Google Patents

Corps moules de detergent a desintegration amelioree Download PDF

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Publication number
EP1037960B1
EP1037960B1 EP98952701A EP98952701A EP1037960B1 EP 1037960 B1 EP1037960 B1 EP 1037960B1 EP 98952701 A EP98952701 A EP 98952701A EP 98952701 A EP98952701 A EP 98952701A EP 1037960 B1 EP1037960 B1 EP 1037960B1
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EP
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Prior art keywords
weight
detergent tablets
detergent
acid
tablets
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP98952701A
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German (de)
English (en)
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EP1037960A1 (fr
Inventor
Monika Böcker
Andreas Lietzmann
Hans-Friedrich Kruse
Michael Feist
Gerhard Blasey
Christian Block
Heinke Jebens
Fred Schambil
Bernhard Müller
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets

Definitions

  • the present invention is in the field of compact moldings, the washing and have cleaning-active properties.
  • the invention relates to washing and Detergent tablets used for washing textiles in a household washing machine used and briefly referred to as detergent tablets.
  • Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage.
  • Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to use and because of their compact size Structure advantages in storage and transportation. Also in the patent literature detergent tablets are therefore comprehensively described.
  • a problem, that occurs again and again when using washing and cleaning active moldings, is the too slow rate of disintegration and dissolution of the shaped bodies under conditions of use. Since sufficiently stable, i.e. shape and break resistant molded articles only can be produced by relatively high pressure, there is a strong Compression of the molded parts and resulting in a delayed disintegration of the shaped body in the aqueous liquor and thus to a slow release the active substances in the washing or cleaning process.
  • the delayed disintegration of the Shaped bodies also have the disadvantage that they are customary shaped detergents and cleaning agents do not allow to wash in via the induction chamber of household washing machines, as the Tablets do not disintegrate into secondary particles that are small enough in a sufficiently quick time are to be washed into the washing drum from the washing-in chamber.
  • EP-A-0 522 766 discloses moldings made from a compacted, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • EP-A-0 716 144 (Unilever), which describes tablets with an external shell made of water-soluble material
  • EP-A-0 711 827 (Unilever), which contain a citrate with a defined solubility as an ingredient.
  • binders which may have an explosive action (in particular polyethylene glycol) is disclosed in EP-A-0 711 828 (Unilever), which describes detergent tablets which are formed by pressing a particulate detergent composition at temperatures between 28 ° C. and the melting point of the binder material be produced, always being pressed below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths when compression is carried out at elevated temperature.
  • the present invention is therefore based on the object of washing and cleaning agent tablets provide the desired properties of high hardness and mechanical Combine stability and nevertheless favorable decay speeds.
  • the invention accordingly relates to molded detergent and cleaning product bodies particulate detergents and cleaning agents, comprising surfactant (s), builders (e) and optionally further detergent and cleaning agent components, the Moldings contain 0.2 to 10% by weight of surfactant (s) from the group of the alkyl polyglycosides and the content of potassium carbonate in the molding is less than 5% by weight.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • x is the degree of glycosidation z reduced by 1 described above, preferred values of x are therefore between 0 and 3, preferably between 0 and 1 and in particular between 0.1 and 0.4.
  • the number n of methylene groups is preferably between 7 and 21, preferably between 11 and 17, carbon atoms.
  • the alkyl polyglycosides used according to the invention can be produced by known processes based on known raw materials. For example becomes dextrose in the presence of an acid catalyst with n-butanol to give butyl polyglycoside mixtures implemented, which with long-chain alcohols also in the presence an acidic catalyst to the desired alkyl polyglycoside mixtures umglycosidiert become. It is also possible to add dextrose directly with the desired long chain alcohol to glycosidate to the desired alkyl polyglycoside mixtures.
  • the structure of the products can be varied within certain limits.
  • the alkyl radical is thereby the choice of long-chain alcohol.
  • the alcohols available from technical alcohol syntheses such as oxo alcohols and Brick alcohols can be used.
  • the polyglycosyl radicals G y are determined, on the one hand, by the selection of the carbohydrate and, on the other hand, by setting the average degree of polymerization (degree of glycosidation y), as is described, for example, in DE 19 43 689 .
  • polysaccharides for example starches, maltodextrins, dextrose, galactose, mannose, xylose, etc. can be used.
  • the commercially available carbohydrates starch, maltodextrins and in particular dextrose are preferred.
  • alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with ⁇ - and ⁇ -glycosidic bonds in pyranose and furanose form. The junctions between two saccharide residues are also different.
  • Alkyl polyglycosides which can be used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
  • alkyl monoglycosides can be obtained or enriched from alkyl polyglycosides using polar solvents such as acetone using the process disclosed in EP 092 355.
  • the degree of glycosidation of alkyl polyglycosides is usually determined by 1 H nuclear magnetic resonance measurements.
  • Detergent tablets according to the invention contain alkyl polyglycosides, where APG contents of the shaped bodies are above 0.2% by weight, based on the entire shaped body, are preferred. Contain particularly preferred detergent tablets APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular from 0.5 to 3% by weight.
  • the detergent tablets according to the invention contain molded articles further surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants, whereby anionic surfactants economic reasons and because of their range of services are clearly preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
  • preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants, including the soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • detergent tablets are preferred the 5 to 60% by weight, preferably 10 to 50% by weight and in particular 20 to 40% by weight anionic surfactant (s), based in each case on the weight of the molding.
  • detergent tablets When selecting the anionic surfactants in the detergent tablets according to the invention are used, the freedom of formulation is not subject to compliance Framework conditions in the way.
  • Preferred detergent tablets however, have a soap content of 0.2% by weight, based on the total weight of the molded body.
  • Anionic surfactants to be used with preference the alkylbenzenesulfonates fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 5 to 15% by weight and in particular 7.5 to 12.5 % By weight of fatty alcohol sulfate (s), based in each case on the weight of the shaped body
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably described in the international patent application Methods described in WO-A-90/13533.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can then, for example, according to the Teaching of the international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
  • builders are the most important ingredients of Detergents and cleaning agents.
  • the detergent tablets according to the invention can all builders commonly used in detergents and cleaning agents be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20, preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula Na 2 O.
  • zeolite (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 to 2.5) SiO 2 ⁇ (3.5 to 5.5) H 2 O can be described.
  • the zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use for ecological reasons is not objectionable, as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Swelling these substances, which are also called “explosives” due to their effectiveness, enlarge their volume when water enters, whereby on the one hand the volume increases (Swelling), on the other hand a pressure can also be generated via the release of gases, which breaks the tablet into smaller particles.
  • Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids also being used can be. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinyl pyrrolidone
  • natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each based on the weight of the molded body.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application PCT / EP 98/1203 (Henkel) , These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.
  • microcrystalline cellulose As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
  • This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses completely dissolve, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent one Disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and, for example can be compacted into granules with an average particle size of 200 ⁇ m.
  • Detergent tablets which are additionally a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, contained are particularly preferred in the context of the present invention.
  • a disintegration aid preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, contained are particularly preferred in the context of the present invention.
  • Detergent tablets are made from powdered components ("Primary particles"), which by means of suitable processes to secondary particles with higher Particle diameter can be agglomerated or granulated. These granules or mixtures different granules are then made with individual powdered additives mixed and fed to the tableting.
  • Primary particles powdered components
  • Preferred detergent tablets in the context of the present invention are obtained by compressing a particulate premix consisting of at least one surfactant Granules and at least one subsequently mixed powdered component receive. It is an advantage for the later detergent tablets, if the premix to be pressed has a bulk density that the usual compact detergent comes close. In particular, it is preferred that the premix to be pressed a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l.
  • the premix Before pressing the particulate premix into detergent tablets the premix can be "powdered” with finely divided surface treatment agents become. This can affect both the nature and physical properties of the Premix (storage, pressing) as well as the finished detergent tablets be an advantage.
  • Fine-particle powdering agents are well known in the prior art, mostly zeolites, silicates or other inorganic salts are used.
  • the premix is preferably "powdered” with finely divided zeolite, zeolites faujasite type are preferred.
  • the term "faujasite type zeolite” means all three zeolites that make up the faujasite subset of the Form zeolite structure group 4 (compare Donald W.
  • zeolites Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily have to belong to the zeolite structure group 4 are used as powdering agents can be used, it being advantageous if at least 50% by weight of the powdering agent consist of a zeolite of the faujasite type.
  • detergent tablets consist of a particulate premix that granular components and subsequently contains powdered substances, the or one of which subsequently admixed powdered components a zeolite of the faujasite type with particle sizes is below 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1 Makes up% by weight of the premix to be pressed.
  • surfactant, builder and disintegration aid can the detergent tablets according to the invention further in detergents usual ingredients from the group of bleaching agents, bleach activators.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaches are, for example, sodium percarbonate.
  • bleach activators compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.
  • Substances containing O- and / or N-acyl groups are suitable carry the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED acylated triazine derivatives
  • Bleaching catalysts can be incorporated into the moldings. Acting on these substances it is bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled already several times beforehand with a detergent according to the invention which is oil and fat dissolving Contains component that has been washed.
  • nonionic cellulose ethers such as methyl cellulose and Methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, the are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • the moldings can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.
  • Farther brighteners of the substituted diphenylstyryl type may be present, e.g.
  • alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
  • Mixtures of the aforementioned brighteners can be used.
  • Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetics Improve impression of the products and the consumer in addition to the softness performance to provide visually and sensory "typical and distinctive" product.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g.
  • benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
  • the linear alkanals with 8-18 Carbon atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal
  • the ketones e.g. the Jonone, ⁇ -Isomethylionon and Methyl cedryl ketone
  • the hydrocarbons mainly include Terpenes like limes and pinene.
  • mixtures of different are preferred Fragrances are used, which together produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures, such as those from plant sources are accessible, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • natural fragrance mixtures such as those from plant sources are accessible, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the dye content of the plasticizers according to the invention is usually lower 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.
  • the fragrances can be incorporated directly into the agents according to the invention, it can but it may also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume reinforce on the laundry and by a slower fragrance release for long-lasting
  • suitable dyes are colored.
  • Preferred dyes their selection to the expert no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards textile fibers so as not to stain them.
  • the moldings according to the invention are first produced by dry means Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing into tablets, whereby conventional Procedure can be used.
  • the premix becomes one in a so-called die between two stamps solid compressed compacted. This process, hereinafter referred to as tableting is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined.
  • the constant dosage even with high molding throughputs, volumetric metering is preferred of the premix reached.
  • the upper stamp touches the pre-mix and lowers further towards the lower punch. With this compression the particles of the premix are pressed closer together, the void volume within the filling between the stamps decreases continuously. From one certain position of the upper stamp (and thus from a certain pressure on the Premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the shaped body.
  • the premixed particles are also crushed and even higher ones occur Press to sinter the premix. With increasing press speed, so high throughputs, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is removed from the lower die the die pressed out and transported away by subsequent transport devices. To At this time, only the weight of the molded body is finally determined, since the Compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.
  • Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure. the lower punch also moves during the pressing process towards the upper stamp while the upper stamp presses down.
  • Production quantities are preferably eccentric tablet presses, in which the or the stamps are attached to an eccentric disc, which in turn is on an axis a certain rotational speed is mounted. The movement of this ram is comparable to the way a conventional four-stroke engine works.
  • the pressing can be done with One upper and one lower stamp are made, but several stamps can be made on one Eccentric disk can be attached, the number of die holes correspondingly expanded is.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to maximum 3000 tablets per hour.
  • rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle.
  • the number of Matrices vary between 6 and 55 depending on the model, although larger matrices are also commercially available are available.
  • Each die on the die table is assigned an upper and lower stamp, where again the pressure is active only through the upper or lower stamp, but also can be built by both stamps.
  • the die table and the stamps move around a common vertical axis, the stamp using rail-like Curve tracks during the circulation in the positions for filling, compression, plastic deformation and ejection are brought.
  • Rotary presses can also be equipped with two filling shoes to increase throughput be, whereby only a semicircle is run through to produce a tablet got to.
  • Several filling shoes are used to produce two-layer and multi-layer molded articles arranged one behind the other without the slightly pressed first layer before further filling is expelled.
  • Appropriate process control also means that and point tablets can be produced, which have an onion-shell-like structure, whereby in the case the tablet is not covering the top of the core or core layers and thus remains visible.
  • Rotary tablet presses are also available with single or multiple tools can be equipped so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs of modern rotary tablet presses amount to over a million molded articles per hour.
  • Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH presses GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU).
  • the hydraulic double pressure press HPF for example, is particularly suitable 630 from LAEIS, D.
  • the moldings can be made in a predetermined spatial shape and a predetermined size become. Practically all sensibly manageable designs come in as the spatial form Consider, for example, the formation as a board, the rod or bar shape, cubes, Cuboid and corresponding spatial elements with flat side surfaces and in particular cylindrical ones Designs with circular or oval cross-section. This last one Design covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality of such mass units connect in a compact, in particular by predetermined breaking points the easy separability of portioned smaller units is provided.
  • For the Use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can form the portioned compacts as tablets, in cylindrical or cuboid shape may be appropriate, with a diameter / height ratio in the area from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, especially for manufacturing such compacts.
  • the spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the molded body can be dosed directly into the induction bowl without a dosing aid, wherever they are dissolves during the induction process. It goes without saying that the Detergent tablets easily possible via a dosing aid and within the scope of the present Invention preferred.
  • Another preferred shaped body that can be produced has a plate-like or sheet-like shape Structure with alternating thick long and thin short segments, so that individual Segments of this "latch" at the predetermined breaking points, which are the short thin segments display, canceled and can be entered into the machine.
  • This principle of the "bar-shaped" shaped body detergent can also be used in other geometric shapes, For example, vertical triangles that are only along one side of their sides are interconnected, can be realized.
  • the various components do not become one Tablet are pressed, but that shaped bodies are obtained which have several layers, thus have at least two layers. It is also possible that these different Layers have different dissolving speeds. This can be advantageous application properties of the moldings result. If, for example Components are contained in the moldings that have a mutually negative effect, so it is possible to integrate the one component in the more quickly soluble layer and incorporate the other component into a slower soluble layer so that the first Component has already reacted when the second goes into solution.
  • the layer structure of the Shaped bodies can be made in a stack-like manner, with a dissolution process of the inner Layer (s) on the edges of the molded body already takes place when the outer layers are not yet fully resolved, but it can also completely wrap the inner Layer (s) can be reached through the layer (s) further out, which leads to prevents premature release of components of the inner layer (s).
  • a shaped body consists of at least three layers, i.e. two outer and at least one inner layer, at least a peroxy bleach is contained in one of the inner layers, while in stack-shaped molded body, the two cover layers and the shell-shaped molded body however, the outermost layers are free of peroxy bleach. It is also possible to Peroxy bleach and any existing bleach activators and / or enzymes spatially separated from each other in a molded body.
  • Such multilayered molded articles have the advantage that they not only have a dispensing chamber or a metering device, which is added to the wash liquor can be used; rather it is in such cases it is also possible to place the molded body in direct contact with the textiles Machine without fear of bleaching from bleach and the like would.
  • the bodies to be coated can be coated, for example, with aqueous Solutions or emulsions are sprayed, or via the process of melt coating get a coating.
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N, which leads to the pressure exerted on the molded body
  • D is the shaped body diameter in meters
  • t is the height of the Moldings.
  • the molded bodies E1 and E2 or V1 and V2 differ only in their hardness, not in their composition. Tables 1 and 2 show the composition of the surfactant granules and the composition of the premixes to be pressed (and thus the moldings).
  • composition of the surfactant granules [% by weight] Granules for E1 / 2 Granules for V1 / 2 C 9-13 alkyl benzene sulfonate 19.4 18.6 C 12-18 fatty alcohol with 7 EO 4.8 5.7 C 12-18 fatty alcohol sulfate 5.2 5.4 C 12-16 alkyl 1,4-glycoside 1.0 - Soap 1.6 1.6 optical brightener 0.3 0.3 sodium 17.0 16.6 sodium silicate 5.6 5.4 Acrylic acid-maleic acid copolymer 5.6 5.4 Zeolite A (anhydrous active substance) 28.5 29.9 Na-hydroxyethane-1,1-diphosphonate 0.8 0.8 Water, salts rest rest Composition of the premix [% by weight]: Surfactant granules 61.3 61.3 zeolite 2.0 2.0 Sodium perborate monohydrate 23.7 23.7 TAED 2.4 2.4 foam inhibitor 4.7 4.7 polyacrylate 1.4 1.4 Perfume 0.5 0.5 Dis
  • the hardness of the tablets was measured by deforming the tablet to break, whereby the force on the side surfaces of the tablet and the maximum force that the Tablet withstood, was determined.
  • the tablet was placed in a beaker with water (600ml water, temperature 30 ° C) and the time taken for the tablet to completely disintegrate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Corps moulés de produits de lavage et de nettoyage à base de produits de lavage et de nettoyage compactés sous forme particulaire, comprenant un (ou des) agent(s) tensioactif(s), une ou (des) substance(s) de squelette ainsi qu'éventuellement d'autres constituants de produit de lavage et de nettoyage,
    caractérisés en ce que
    les corps moulés renferment de 0,2 % à 10 % en poids d'agent(s) tensioactif(s) choisi(s) dans le groupe des alkylpolyglycosides et la teneur des corps moulés en carbonate de potassium se situe en dessous de 5 % en poids.
  2. Corps moulés de produits de lavage et de nettoyage selon la revendication 1,
    caractérisés en ce que
    ils renferment de 0,2 % à 5 % en poids de préférence de 0,5 à 3 % en poids d'APG à chaque fois rapportés au poids de corps moulés.
  3. Corps moulés de produits de lavage et de nettoyage selon l'une des revendications 1 ou 2,
    caractérisés en ce que
    l'APG contenu dans ceux-ci, possède un degré de glycosidation allant de 1,0 à 4,0, de préférence de 1,0 à 2,0 et en particulier de 1,1 à 1,4.
  4. Corps moulés de produits de lavage et de nettoyage selon l'une des revendications 1 à 3,
    caractérisés en ce que
    comme APG on met en oeuvre un alkylpolyglucoside.
  5. Corps moulés de produits de lavage et de nettoyage selon la revendication 4,
    caractérisés en ce que
    un adjuvant de désintégration à base de cellulose, en supplément est contenu dans les corps moulés en quantités allant de 0,5 à 10 % en poids.
  6. Corps moulés de produits de lavage et de nettoyage selon l'une des revendication 1 à 5,
    caractérisés en ce qu'
    ils ont été obtenus par compression d'un prémélange sous forme particulaire à base d'au moins un granulé contenant un agent tensioactif et au moins un composant pulvérulent ajouté ultérieurement par mélange.
  7. Corps moulés de produits de lavage et de nettoyage selon la revendication 6,
    caractérisée en ce que
    le prémélange à comprimer possède une densité apparente d'au moins 500 g/l, de préférence d'au moins 600 g/l et en particulier au-dessus de 700 g/l.
  8. Corps moulés de produits de lavage et de nettoyage selon l'une des revendications 6 ou 7,
    caractérisés en ce que
    le composant pulvérulent ou un des composants pulvérulents ajoutés ultérieurement par mélange est une zéolithe du type Faujasite ayant des tailles de particules en dessous de 100 µm, de préférence en dessous de 10 µm et en particulier en dessous de 5 µm et représente au moins 0,2 % en poids, de préférence au moins 0,5 % en poids et en particulier plus de 1 % en poids du prémélange à comprimer.
  9. Corps moulés de produits de lavage et de nettoyage selon l'une des revendications 1 à 8, qui contiennent en outre plusieurs substances choisies dans le groupe des substances de squelette, des agents de blanchiment, des activateurs de blanchiment des enzymes, des produits de réglage du pH, des parfums, des vecteurs de parfum, des agents de fluorescence, des colorants, des agents anti-mousse, des huiles de silicone, des agents anti-redéposition, des éclaircissants optiques, des inhibiteurs de grisaillement, des inhibiteurs de conversion des couleurs et des inhibiteurs de corrosion.
EP98952701A 1997-12-08 1998-10-08 Corps moules de detergent a desintegration amelioree Expired - Lifetime EP1037960B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19754289 1997-12-08
DE19754289A DE19754289A1 (de) 1997-12-08 1997-12-08 Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
PCT/EP1998/006405 WO1999029826A1 (fr) 1997-12-08 1998-10-08 Corps moules de detergent a desintegration amelioree

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EP1037960B1 true EP1037960B1 (fr) 2002-08-28

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JP (1) JP2001526306A (fr)
AT (1) ATE222948T1 (fr)
DE (2) DE19754289A1 (fr)
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WO (1) WO1999029826A1 (fr)

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Publication number Priority date Publication date Assignee Title
US6369021B1 (en) * 1999-05-07 2002-04-09 Ecolab Inc. Detergent composition and method for removing soil
WO2002033036A1 (fr) * 2000-10-18 2002-04-25 Unilever N.V. Composition de lavage
DE10118270A1 (de) * 2001-04-12 2002-10-17 Cognis Deutschland Gmbh Wasch- und Reinigungsmittelformittelkörper mit verbesserten Zerfallseigenschaften
DE10202390A1 (de) * 2002-01-23 2003-09-25 Henkel Kgaa Kombination von Cellulasen und spezieller Cellulose in Waschmitteln
DE102011119332A1 (de) 2011-11-25 2013-05-29 Centrum Für Angewandte Nanotechnologie (Can) Gmbh Verwendung von über radikalische Emulsionspolymerisation erhältlichen Polymeren als Verdicker für Reinigungsmittel
CN104418920B (zh) * 2013-08-23 2016-11-16 河北科技大学 采用一步法连续生产烷基糖苷的方法和系统
CN107460060A (zh) * 2017-08-17 2017-12-12 成都新柯力化工科技有限公司 一种胶束渗透型浓缩快速洗衣液及制备方法
CN110305742A (zh) * 2019-07-12 2019-10-08 广州立白企业集团有限公司 一种自动洗碗机洗涤剂组合物

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JP2756033B2 (ja) * 1990-10-29 1998-05-25 花王株式会社 錠剤型洗剤
JPH06108099A (ja) * 1992-09-30 1994-04-19 Lion Corp タブレット洗剤組成物
GB9224015D0 (en) * 1992-11-16 1993-01-06 Unilever Plc Detergent compositions
DE19509752A1 (de) * 1995-03-17 1996-09-19 Henkel Kgaa Verfahren zur Herstellung eines pulverförmigen Waschmittels
DK173111B1 (da) * 1996-04-03 2000-01-31 Cleantabs As Tøjvasketabletter

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EP1037960A1 (fr) 2000-09-27
ES2181286T3 (es) 2003-02-16
WO1999029826A1 (fr) 1999-06-17
DE59805352D1 (de) 2002-10-02
DE19754289A1 (de) 1999-06-10
ATE222948T1 (de) 2002-09-15
JP2001526306A (ja) 2001-12-18

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